Process for the production of dyestuffs



United States Patent 6 Claims. (Cl.260--314.5)

ABSTRACT OF THE DISCLOSURE Novel dyestuffs which have the general formula:

wherein Fe is a metal-containing phthalocyanine radical, R is a hydrogen atom, a lower alkyl or lower hydroxyalkyl group, z is 1 or 2, y is l, 2, or 3, R and R which may be the same or different, are hydrogen atoms or lower alkyl radicals, Alk is an alkylene chain containing two or three carbon atoms and R is an alkyl radical containing 6 to 14 carbon atoms, are prepared by reaction of metal containing phthalocyanine containing at least one free sulphonic acid group with an amine. The dyestufls are of particular utility in the preparation of inks.

DISCLOSURE The present invention is concerned with new dyestuffs of the phthalocyanine series and with the production thereof.

We have found that valuable dyestuffs of the phthalocyanine series are obtained when metal-containing phthalocyanines which contain free sulphonic acid groups and at least One sulphonamide group, the amide nitrogen of which is subsituted by one or two hydroxyalkyl groups, are reacted with amines of the general formula:

wherein R and R which may be the same or different, stand for hydrogen atoms or a lower alkyl radicals, Alk stands for an alkylene chain containing two or three carbon atoms, and R stands for an alkyl radical containing six to fourteen carbon atoms.

The metal-containing phthalocyanines to be used according to the present invention as starting materials may contain, for example, copper, nickel or cobalt. These phthalocyanines preferably contain one to three sulphonic acid groups which may be in the 3- or 4-position of the phthalocyanine molecule. The sulphonamide group is likewise linked directly with the phthalocyanine molecule and may also be in the 3- or 4-position of the phthalocyanine molecule. The amide nitrogen of the sulphonamide group may contain one or two alkyl groups with the proviso that at least one a-lkyl group contains at least one hydroxyl group. The alkyl radical may, however, also contain several hydroxyl groups, for example, two or three hydroxyl groups. These alkyl radicals preferably contain up to 6 carbon atoms.

Patented Jan. 23, 1968 Examples of hydroxyalkyl groups of this type are 2- hydroxy-ethyl, 3-hydroxy-propyl, 1,3-dihydroxyisobutyl, 3-hydroxy-butyl, trihydroxy-isobutyl and G-hydroxy-nhexyl radicals.

Examples of amines of the specified type are: 3-(2'- ethylhexoxy) propyl 1 amine, 3 (hexoxy) propyl- 1 amine, 3 (3,5',5" trimethylhexoxy) propyl lamine and the amine which is obtained by the condensation of tri-isodecanol with acrylonitrile and reduction of the nitrile group. (In this context the term tri-isodecanol refers to the C alcohol mixture which is obtained by condensing 3 mol butylene and subjecting the condensation product to an oxo synthesis.)

The production of the new dyestuffs obtained according to the present invention is carried out by reacting the phthalocyanine-sulphonic acids containing hydroxyalkylsulphon-amide groups, or their alkali metal salts, with the amines or their salts, such as the acetates or hydrochlorides. The reaction is preferably carried out in an aqueous solution or suspension, but it is also possible to operate in other inert solvents, for example, alcohols. If the reaction is carried out in an aqueous medium, it is expedient to maintain the pH value of the reaction mixture obtained below 7 in order to prevent the reaction products from sintering together. The amines are expediently used in amounts suflicient for all free sulphonic acid groups to be converted into the corresponding amine salts, but it is also possible to Work with an excess of amine.

The dyestutfs obtained have a particularly good solubility in polyglycols. On the other hand, the compounds are insoluble or only hardly soluble in water. The dye stuff salts according to the present invention are particularly well suited for the production of pastes for ball point pens based on polyglycols.

The following examples are given for the purpose of illustrating the present invention, the parts being by weight:

Example 1 57.5 parts copper-phthalocyanine are dissolved in 205 parts chlorosulphonic acid, while slowly raising the temperature to 130 C. The reaction mixture is stirred at 136 to 138 C. for one hour. Stirring is subsequently continned at 136 to 138 C. for 2 hours, the melt is cooled to to C. within the course of one hour and stirred at 90 to 95 C. for one hour. During this reaction time of 4 hours, 98 parts thionyl chloride are allowed to run in continuously. The reaction mixture is then stirred at 90 to 95 C. until the formation of the sulphochloride is completed. After cooling, the melt is poured on to ice and the copper-phthalocyanine3,3,3",3'-tetrasulphochloride is filtered off with suction and washed with ice water until neutral.

The sulphochloride paste thus obtained is slurried in 1000 parts water. 11 parts propanolamine and ().6 part pyridine are then added. To form the sulphamide, the reaction mixture is stirred at 20 to 25 C., while slowly adding parts of an 1 N sodium hydroxide solution and maintaining the pH value of the suspension at 9.0 to 9.6. When the reaction is completed, the mixture is heated to 80 C. and the residual sulphonic acid chloride groups are hydrolysed with a sodium hydroxide solution. After acidification with hydrochloric acid, the precipitated copper-phthalocyanine-sulphonic acid is filtered ofi with suction, thoroughly washed with dilute hydrochloric acid and dried.

49 parts 3-(2'-ethylhexoxy)-propyl-1-amine are dissolved in 1000 parts water, with the addition of acetic acid, and the solution is adjusted to a pH value of 7.5. To this solution there is slowly added, while stirring, a solution of the copper-phthalocyanine-sulphonic acid obtained above, and substituted by hydroxy-propyl-sulphamide 3,365,463 3 4 groups, in 1000 parts water. The suspension obtained is cyanine 3,3,3" monohydroxy-propylamido-disulphonic subsequently stirred at 50 to 60 C. for a further 1 to 2 acid thus obtained in good yield is dried at 70 to 80 C. hours, suction-filtered and the filtered material washed The dyestufi' is excellently soluble in polyglycols; it can be with 1500 parts water and dried at 70-80 C. characterised by the following formula:

(3) (SOz-NHC Hg-C Hg-CH10 H)1 CuPc CzHi (3',3) SOaH.H;NCH;CIIzCH1O-CHz-CH 04H? 1 The dyestuif thus obtained in excellent yield dissolves Similar dyestuffs are obtained when the propanol-1,3- in 2 to 3 parts by volume of polyethylene glycol. The dyediainine used in paragraph 2 is replaced by equimolecular stuff obtained can be characterised by the following foramounts of ethanolamine or butanol-l,3-diamine. mula:

lWhen the propanolamine used in paragraph 2 is re- Example 3 p aced by equimolecular amounts of ethanolarnine or butanol-l,3-diamine, dyestuffs of similar solubility in poly- 50 Parts 3'(2'ethylhexoxy)'pr'opyll'flmme a d118- ethylene glycol am Obtained. solved 1n 1000 parts water with acetrc acid and e 50 ution 1s ad usted to pH 7.5. To this solultion there is slowly Example 2 added, while stirring, a solution of parts copper- 30 phthalocyanine-3,3,3" dihydroxypropyl sulphamidomonosulphonic acid and 68 parts copper-phthalocyanine- 3,3',3"-monohydroxy propyl sulphamindo-disulphonic 57.6 parts copper-phthalocyanine are dissolved in 210 parts chlorosulphonic acid, while slowly raising the temperature to 110 C. The melt is subsequently stirred at 113 t 115 C il approximately 3 sulphonic acid or acid in 2000 parts water. The reaction mixture is subsulpho-chloride groups have entered into the phthalocyaq y further Stirred for 2 hours at t0 and nine molecule. 65 parts thionyl chloride are then allowed the Product Suction filtered and washed With Watfif- The to run in within the course of 2 hours, while stirring. dyestufi is excellently Soluble in p y y It is When the formation of the sulpho-chloride is completed, nemly Suitable the Production of ball point P pastes the reaction mixture is cooled and the melt poured on to based on polyglycols. The dyestutf can be characterised by ice. The precipitated co pper-phthalo cyanine-3,3 ,3"-trisul- 40 the following formula:

(3)-so ,N II-C H -C HzC Hz-0 H 70% CuPc C 1H5 (3,3") SO H.HiNCHz-C HnC Hz-O-C Hr-C H C 4H9 1 (3,3) (so =NHO Hz-C I-I,C 11,-0 H) +30% Culc C2115 (3)S0 H.H N-CHiCHiCH;O-CH;CH

phonic acid chloride is filtered off with suction and washed Example 4 with ice water until neutral.

The copper-phthalocyanine-sulphonic acid chloride The sulphonic acid chloride paste of copper-phthalopaste thus obtained s slurried in 1000 parts water. 8.2 cyanine-3,3',3",3"-tetrasulphonic acid chloride obtained parts propanol-l,3-d1am1ne and 0.5 part pyridine are according to paragraph 1 of Example 1, is slurried in 1000 subsequently added. 110 parts 1 N sodium hydroxide soluparts water 11 parts 1-1,3-dia ine and 0,6 parts tion are then added at 20 to 25 C. with stirring so that pyridine are then added. To form the sulphamide, the rethe pH value of the suspension 15 about 9.0 to 9.6. When action mixture is Stirred at 20 to While slowly the formation of sulphamide is completed, the reaction adding 150 parts 1 N Sodhlm h droxide Solution and mixture is heated to 80 C. The residual sulphonic acid maintaining the PH value the 3 ension at 9 0 to 9 6 Y E 'F P hiidrolyseq by the addition of Sodium When the reaction is completed a]: reaction mixture is Y ro' t t 3 M 6 so u Ion Tm reac mlxture 18 Subsequently heated to 80 C. and the residual sulphonic acid chloride acidified and the precipitated copper-phthalocyanine-3,3, 3,, monohydmXypmPyLsmphamido disulphonic acid is groups are hydrolysed with a sodium hydroxide solution.

tered off with suction, washed with dilute hydrochloric The reaction mixture is 600164 to 20 t0 and acidiacid, and dried. fied with hydrochloric acid until the pH is 2.0 3-(2- 37 parts 3-(2'-ethylhexoxy)-propyl-1-amine are disethylhexoxy)-propyl-1-arnine is then slowly added with Solved in 1000 p f f with the addition of acetic stirring until the pH value of the suspension has reached acld, and the Solunon adlusted to PH The Copper 5.5 to 6.0. Stirring is continued at a slightly elevated temphthalocyanine 3,3,3" monohydroxyp-ropyl-sulphami- -d' l h d bta'n d b0 and d sol d 2000 gz i g g f i j gg The E i i then with suction, washed with water and dried at 70 to 80 C.

further stirred at 50 to 60 C. for several hours and the The dyestulf Obtained in excellent yield is exctinemly product is suction-filtered and washed with water. The 301111915 in p yg y It has the formula given in 3-(2-ethyl)-hexoxypropyl-1-amine salt of-copper-phthalo- Example 1.

perature for several hours and the product is filtered off Example 5 67 parts 3-(tri-iso-decyloxy)propyl-l-amine are dissolved in 1000 parts water, with the addition of acetic acid, and the solution is adjusted to a pH value of 5.6. To this solution, there is slowly added, while stirring, a solution, in 1000 parts water, of the copper-phthalocyanine-sulphonic acid, substituted by hydroxypropylamide groups and obtained according to paragraph 2 of Example 1. The suspension obtained is further stirred at to C. for l to 2 hours and the product is filtered off with suction, washed with 1500 parts water and dried. The dyestutf obtained in excellent yield dissolves in 2 parts polyethylene glycol and is eminently suitable for the production of ball point pen pastes based on polyglycol. The dyestuff can be characterised by the following formula:

3000 parts water and slowly added to a solution of 49 parts 3-(2'-ethylhexoxy)propyl-l-amine in 1000 parts water, which had been adjusted to pH 7.5 by means of acetic acid. The suspension obtained is further stirred at 50 to 60 C. for 1 to 2 hours. The product is then filtered off with suction and the filtered material is washed with water and dried. The dyestuff obtained in excellent yield is readily soluble in polyglycols and eminently suitable for the production of ball point pen pastes based on polyglycol. The dyestutf can be characterised by the following 37 parts of an alkyl resin prepared from 42% castor oil, 39% phthalic anhydride and 19% glycerol, are mixed at to 100 C. with 38 parts of a polyethylene glycol 25 Example 7 Example 6 96.7 parts copper-phthalocyanine-(4,4',4",4")tetrasulphonic acid chloride (obtained from copper-phthalocyanine-(4,4',4",4"')tctrasulphonic acid or its sodium salt, chlorosulphonic acid and thionyl chloride at 80 to C.) in the form of an aqueous paste, are slurried in 1500 parts ice water. 11 parts propanolamine and 0.5 part pyridine are then added. 1500 parts 1 N sodium hydroxide solution are slowly added, with stirring, while slowly raising the temperature to 20 C. and maintaining the pH value of the suspension at 8 to 9. When the sulphamide formation is completed, the reaction mixture is heated to 80 C. and the residual sulphonic acid chloride groups are hydrolysed with sodium hydroxide solution. To isolate the reaction product, the solution is stirred into dilute hydrochloric acid and the sulphonic acid is filtered off with suction, washed with dilute hydrochloric acid and dried.

The reaction product of paragraph 1 is dissolved in with an average molecular weight of 300 until the dispersion is satisfactory. 25 parts of the blue dyestufi produced according to Example 1 are dissolved in this mixture. The dyestutf solution thus prepared yields an excellent ball 40 point pen paste which is fast to light.

Example 8 (a) If in the procedure described in Example 1 there are used 8 parts of propanolamine-(1,3) and 56 parts of 3-(2'-ethylhexoxy)propyl-l-amine then there is obtained a dyestuff of the folowing formula in good yields:

7 8 The dyestufls show an excellent solubility in polyethylene wherein Fe is a metal-containing phthalocyanine radical, glycol. wherein the metal is copper, nickel, or cobalt, R is a hydrogen atom, a lower alkyl or lower hydroxy-alkyl group, X is a hydroxyalkyl group of 2 to 6 carbon atoms, 2 is 1 (a) If in the process described in Example 1 there are 5 or y 15 2 or R1 and whlch may be the f used 16 arts of m anolamine and 37 arts of or d fferent, are hydrogen atomsor lower alkyl radlcals,

P P P p Alk is an alkylene cham containlng two or three carbon Y Y)-P PY then there 15 Obtamed atoms and R is an alkyl radical containing six to four- Example 9 in good yield the dyestufi? of the formula: teen carbon atoms.

(3,3)-(SO2NHC H -C El -C H20 H),

CuPc z s (3",3) SOzH-HzN-CH -CHCH;OCH;CH

2. Dyestulf of the formula:

(3)-SO1NHC Hr-C HzCHz-OH CuPc 021-1 (3',3,3") s 0 3HHgNC H -C Hz-C Hr-O-C m-o 11 3. Dyestutf of the formula:

(3,3)(s0,NHCH1-C H1C Hz-O H) CuPc C2115 (3",3')- SO3H-HgN-CH:CH1-CHr-O-CHg-Cli The dyestuff shows an excellent solubility in polyethylene 4. Dyestufi of the formula: glycol.

(3)'SO1NH CH2 CH2 C1'I2OH CuPc /C;H5

(3,3) SO3H-H N-C HgC H1C Hz-O-C H1C H (b) If the process described in Example 9(a) is carried out by using 12 parts of ethanolamine respectively in a 40 5. DyestufI of the formula:

second procedure 14 parts of 3-aminobutanol-1 instead of the 16 parts of propanolamine-l then the following 50 dyestuffs are obtained:

The dyestuffs show an excellent solubility in polyethylene glycol.

What we claim is:

1. A phthalocyanine dyestuif of the formula:

9 10 6. Dyestuff of the formula:

References Cited UNITED STATES PATENTS 3,082,213 3/1963 Pugin et a1. 260314.5 3,057,873 10/1962 Pugin et a1 260314.5

WALTER A. MODANCE, Primary Examiner. H. I. MOATZ, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,365 ,463 January 23 1968 Manfred Groll et al It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 5, line 43, "1500" should read 150 Column 6, line 26, "alkyl" should read alkyd Column 6, Example 8(b) Column 7 Example 9 (a) Example 9 (b) Column 8 Claims 2 3 4 and 5, that portion of the formula reading "SO H-H N", each occurrence should read SO FLH N Column 8, lines 44 to 46, the left-hand portion of the formula should appear as shown below:

C H Z 5 CH Signed and sealed this 30th day of September 1969.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR Attesting Officer Commissioner of Patents 

